How to prepare acetals from olefins using PtI2 or PtBr2

Abstract

To provide a process for preparing an acetal from an olefin in good yield.SOLUTION: The process comprises the steps of: a) initially introducing an olefin; b) adding a phosphorus compound such as Xantphos; c) adding PtI2 or PtBr2; d) adding an alcohol selected from among methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, and butane-1,4-diol; e) feeding in CO and H2; f) heating the reaction mixture from the steps a) to e) so as to convert the olefin to an acetal.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for preparing acetals from olefins using PtI2 or PtBr2. Summary of the Invention [Problem to be solved by the invention]

[0002] The object of the present invention was to provide a process for preparing acetals from olefins, the intention here being to achieve good yields. [Means for solving the problem]

[0003] This object is achieved by a method according to claim 1.

[0004] a) initially charging an olefin; b) Formula (I):

[0005] [ka]

[0006] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 -H, -(C1-C 12 )-Alkyl, -(C6-C 20 )-aryl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Ga-(C6-C 20 )-aryl, the aryl ring is -(C-C 12 )-alkyl, -O-(C1-C12 )-alkyl. and adding a compound of the formula: c) adding PtI2 or PtBr2; d) adding an alcohol selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol; e) providing CO and H2; f) heating the reaction mixture of steps a) through e) to add the olefin to the acetal; A method comprising:

[0007] In this method, steps a) to e) can be carried out in any order, although typically, in steps a) to d), the co-reactant is first charged, followed by the addition of CO and H.

[0008] Expression (C1-C 12 )- includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl groups, more preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl.

[0009] Appropriate (C1-C 12)-Alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

[0010] Expression (C6-C 20 )-aryl includes monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C-C 10 )-aryl.

[0011] Appropriate (C6-C 20 )-aryl groups are in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. Preferred (C-C 20 )-aryl groups are phenyl, naphthyl and anthracenyl.

[0012] In one variation of this method, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is -(C1-C 12 )-Alkyl, -(C6-C 20 )-aryl.

[0013] In one variation of this method, R 5 , R 6 , R 7 , R 8 is -(C6-C 20 )-aryl.

[0014] In one variation of this method, R 5 , R 6 , R 7 , R 8 is -Ph.

[0015] In one variation of this method, R 2 and R 3 is -(C1-C 12 )-alkyl.

[0016] In one variation of this method, R 2 and R 3 is -CH3.

[0017] In one variation of this method, R 1 and R 4 is -H.

[0018] In one variation of the method, compound (I) has the structure (1):

[0019] [ka]

[0020] It has.

[0021] In one variation of the method, PtI2 is added in step c).

[0022] In one variation of the method, PtBr2 is added in step c).

[0023] In one variant of the process, the alcohol of step d) is selected from methanol, ethanol, 1-propanol, 1-butanol, ethane-1,2-diol, propane-1,2-diol.

[0024] In one variation of the method, the alcohol in step d) is MeOH.

[0025] In one variation of the method, CO and H2 are supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

[0026] In one variation of the method, CO and H2 are supplied at a pressure in the range of 3 MPa (30 bar) to 5 MPa (50 bar).

[0027] In one variant of the process, the olefin is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, tri-n-butene, 1,7-octadiene, 1,9-decadiene, methyl 9-decenoate (9-Dame) or mixtures thereof.

[0028] In one variation of the method, the olefin has two double bonds.

[0029] In one variation of the method, the olefin has two terminal double bonds.

[0030] In one variation of the process, the olefin is 1,3-butadiene.

[0031] In one variation of the method, the reaction mixture is heated to a temperature in the range of 50°C to 150°C.

[0032] In one variation of the process, the reaction mixture is heated to a temperature in the range of 80°C to 140°C.

[0033] In one variant of the method, the method comprises an additional step e') of adding a solvent that is not an alcohol.

[0034] In one variant of the process, the solvent is selected from THF, MTBE, DCM, ACN, heptane, DMF, toluene, xylene, mesitylene, dibenzyltoluene.

[0035] The present invention will be explained in detail below with reference to examples. [Example]

[0036] General Experimental Instructions Olefin, inert solvent, alcohol, PtX2 (X = halogen), and ligand were placed in a Parr Instruments stainless steel autoclave under an argon atmosphere. Syngas CO / H2 (1:1) was injected and the reaction was carried out with stirring at the selected reaction temperature. After the reaction time was over, the autoclave was cooled to room temperature, the residual pressure was released, and a GC sample was taken and analyzed to determine the yield of the desired product.

[0037] Olefin Variation: 1-Octene Reaction conditions: 10 mmol of 1-octene, 0.5 mol% of PtI2, 2.2 equivalents of Xantphos (1), solvent: toluene, pressure p(CO / H2): 40 bar, temperature T: 80 °C, time t: 24 h. Monoalcohol: 4 equivalents; Diol: 2 equivalents

[0038] [Table 1]

[0039] Alcohol Variation: 1,3-Butadiene Reaction conditions: 10 mmol of 1,3-butadiene, 0.5 mol% of PtI2, 2.2 equivalents of Xantphos (1), solvent: toluene, pressure p(CO / H2): 40 bar, temperature T: 80°C, time t: 24 hours. Monoalcohol: 4 equivalents; Diol: 2 equivalents

[0040] TIFF0007730397000004.tif126170

[0041] Halogen variations

[0042] [ka]

[0043] 10 mmol of 1-octene, 40 mmol of methanol, 10 mL of toluene, PtX2 (0.1 mol%), and Xantphos (1) (0.22 mol%) were introduced into a 25 mL autoclave under argon. Synthetic gas (CO / H2 = 1.1) was injected up to 40 bar. The reaction was carried out for 24 h with stirring at 120 °C, while measuring the gas consumption in the autoclave (electronic pressure transducer, Specview software). The autoclave was cooled to room temperature and the pressure was released. GC samples were taken to determine the yield. The reaction was carried out with X=I / Br / Cl.

[0044] Reaction conditions: 10 mmol of 1-octene, 0.1 mol% of PtX2, 2.2 equivalents of Xantphos (1), solvent: toluene, pressure p(CO / H2): 40 bar, temperature T: 120°C, time t: 24 hours.

[0045] yield: PtI2: 46% PtBr2: 36% PtCl2*: 7% *Non-inventive comparative experiment

[0046] As can be seen from the experimental results, the method of the present invention achieves the objective.

Claims

1. a) initially charging an olefin; b) Formula (I): 【Chemical 1】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ is -H, -(C １ -C １２ )-alkyl, -(C ６ -C ２０ )-aryl; R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ But-(C ６ -C ２０ )-aryl, the aryl ring is -(C １ -C １２ )-alkyl, —O—(C １ -C １２ )-alkyl. and adding a compound of the formula: c) PtI ２ or PtBr ２ and adding d) adding an alcohol selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol; e) CO and H ２ and f) heating the reaction mixture of steps a) through e) to convert the olefin to an acetal; A method comprising:

2. R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ is -(C １ -C １２ )-alkyl, -(C ６ -C ２０ 2. The method of claim 1, wherein the aryl is selected from the group consisting of aryl, ...

3. R ５ , R ６ , R ７ , R ８ is -(C ６ -C ２０ 2. The method of claim 1, wherein the aryl is aryl.

4. R ２ and R ３ is -(C １ -C １２ 2. The method of claim 1, wherein the aryl group is aryl.

5. R １ and R ４ The method of claim 1 , wherein is —H.

6. The compound (I) has the structure (1): 【Chemistry 2】 2. The method of claim 1, comprising:

7. PtI ２ is added in step c).

8. PtBr ２ is added in step c).

9. 2. The method of claim 1, wherein the alcohol in step d) is selected from methanol, ethanol, 1-propanol, 1-butanol, ethane-1,2-diol, propane-1,2-diol.

10. 2. The method of claim 1, wherein the alcohol in step e) is MeOH.

11. CO and H ２ The method of claim 1, wherein is supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

12. CO and H ２ The method of claim 1, wherein is supplied at a pressure in the range of 3 MPa (30 bar) to 5 MPa (50 bar).

13. 2. The process of claim 1, wherein the olefin is selected from ethene, propene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, tri-n-butene, 1,7-octadiene, 1,9-decadiene, methyl 9-decenoate (9-Dame), or mixtures thereof.

14. The method of claim 1 , wherein the olefin has two double bonds.

15. The method of claim 1 , wherein the olefin has two double terminal bonds.

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